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Reissued Apr. 3, 1928.

v UNITED v STATES,

Re. 16,921 PATENT oFFIcE.

mortars same xrmnnscn, OFICOLLEGE PARK, MARYLAND.

WATER-SOLUBLE METALLIC ORGANICCOMPOUND AND PROCESS OF MAKING THE SAME.

" 1V0 Drawing. Original No. 1,589,599, dated-June 22,1926, Serial No. 708,807, filed April 24, 1924.

Application for reissue flled'June 16, 1927. Serial No. 199,413.

as compounds of mercury, arsenic, antimony,

bismuth and the like, the efliciency of which have hitherto been greatly limited by the difliculty of producing readily soluble compounds.v In carrying out the process of my invention, I react upon an organo-metallic compound with a suitable organic compound.

which is either water soluble or has water soluble salts and which contains the thio-' hydroxyl group (SH). The initial organic metallic compound used may have the general formula (It-) M(-w) in which R is any organic group having .the metal attached to a carbon atom, a: is any replace 3 able inorganic roup of other than the sulphur family, L? is any metal which has a valence greater than 1 and which will form organo-metallic compounds stable toward water and with the metal bondedto a carbon :5 atom, and n and n are each integers greater than zero and at least one less than the valence of the metal. The initial thiohydroxyl compound used is of the general formula H-S-R,,, in which R is an or- 40 anic radical containing an acid group and having a carbon atom directly bonded to S; or a soluble salt of'the acid shown by that eneral formula. In other words, the initial t iohydroxyl compound used contalns the;

thiohydroxyl group 'SH with the sulphur atom bonded to an acid-forming organic radical which when so bondedstill has a se arate valence bond capable of combining w th a positive ion hydro'gen or a metal- 5 and which if joined to hydrogen forms an acid or if joined to sodium or potassium I formsthe corresponding salt. Thus I may use the alcohols such as ethyl mercaptan,

thioglycerine, or thioglycol, or carboxylic compounds, such as thioglycollic acid, thio lact c acid, thiomalic acid, thiosalicylic acid, etc., or their salts; or analogous sulfonic compounds; or thiophenols, such as thioresorc1ono1, thionaphthol; and like products.

A typical formula for the initial organometallic compounds is as follows: RHgw in which R is any organic radical havin the Hg attached to a carbon atom and in Vllflh :0 1s any replaceable inorganic radical or group. Hg can be replaced by any metal havlnga valence greater than one which will form organo-metallic compounds with the metal bonded to a carbon atom and which compounds are stable toward water. These metals are in general those lying lower than hydrogen in the electro-motive series.

By the general process outlined,-I may tain organo-metallic compounds, or salts thereof, of the following general formula:

rtn. M('-s RA, in which R, M, R n, and n are as above described. Some of the acids themselves are water-soluble, and all the sodium and p0- tassium salts thereof are water-soluble. The following specific examples illustrate the invention:

Example 1.

Phenyl mercury chloride, C,,I-I,,.HgCl, is

treated with potassium thioglycollate, HS'CH COOK.. The potassium thioglycollate, which is water soluble, is first dis-' mercury compound passes readily into solu-- tion, apparently as the compound having the formula C H, ,Hg-S-CH,'COOK. The following reaction takes place CJLHgCl HS-CH COOK-r To neutralize the hydrochloric acid resultbe added to the solution.

any other acid may be added. A white ing from the above reaction the requisite amount of sodium bicarbonate, NaI'ICO may To purify the product thus formed, hydrochloric acid or precipitate is formed which is I This substance melts, with decomposition, at 164 C. This may be collected on a filter, washed well with water to remove any inorganic salts, dried in a desiccator and then dissolved in the calculated amount of sodium or potassium hydroxide and 'the whole poured into 95% alcohol. The salt separates andis collected on a filter. This salt is water-soluble.

Example 2.

\ o I I To a concenti'ated water solutlon containin 0.1 mole of the sodium salt of thiosalicy ic acid, the equivalent amount of plienyl mercuric chloride is added and the whole heated for 15 minutes, when the phenyl mercuric chloride goes into solution in the form The addition of a .small amount of sodium carbonate is quite beneficial for it neutralizes the hydrochloric acid formed in the reaction.

ab 013 2 0H3 The alcoholicsolution is then evaporated to dryness in vacuo. The residue is treated with water and then a small amount of acetic acid is added. The precipitate thus obtained is washed well with water and collected on the filter and then dissolved in the concentrated solution of one equivalent of sodium hydroxide and the whole poured into a mixture of alcohol and ether. The followingsalt separates:

011.03, aEst scngcooua The compoundthus obtained is soluble in water, insoluble in alcohol-ether mixture, insoluble in benzene and other common organic solvents. Upon boilin for a long time in water the solution is iroken down. It has no melting point.

Emwmple 4.

To an alcoholic solution of phenyl arseni ous chloride an e uivalent amount of the potassium salt of t iogl collic acid is added and the whole warme for about five min- The compound thus obtained, namely may be purified by treating the water solution with an acid. A compound B-HgC|H; separates which can be collected on a filter and washed free from all impurities. The precipitate can then be dissolved in the calculated amount of a sodium hydroxide solution and the latter poured into 95% alcohol.

S-r-HI-CgH separates. This product is water soluble.

The salt has no melting point and is insoluble in ether, alcohol, and other organic solvents. When boiled for a long period of time, particularly in concentrated solution, mercuric sulfide separates. The free acid of this salt may be obtained by the addition of any strong acid.

F Emample 3;

To an alcoholic solution of p-tolyl antimony chloride the? equivalent amount of sodium or potassium salt of thioglycollic acid is added and the whole warmed for five minutes on a water bath. The following compound is produced:

utes on a water bath. The following com pound is produced c,H..AS 012 2(HS- oH, .cooK

oat (SCH,.GOOK),+2HC1 The compound can be purified in exactly .the same manner as outlined in case of the antimony compound given in Example 3, namely the formation of the free acid and the later reparation of the salt. It has no definite p ysical characteristics.

. spirit of the invention.

I claim: 1. The step in the process of producing water soluble metallo-organic compounds which comprises treating with a, solution of an organic compound containing a thio-hydroxyl group directly attached to a carbon atom a compoundof the formula RMw in which R is any organic radical havinglthe .metal attachedto a carbon atom, in w ich a! is any replaceable inorganicradical or grou and in which M is any metal having a va ence greater than one which will form organo-metallic compounds with the metal bonded to a carbon atom, stable toward water. a

2. The method of producing a water soluble metallo-organic compound which comprises treating with a solution of a salt of an organic thio-hydroxyl compound havin its thio-hydroxyl group directly attache to a car on atom 'and containing an acidoup a compound of the formula R- -a: in which R is any organic radical having the metal attached to a carbon atom, in which :a is any replaceable inorganic radical or group, and in which M is any metal having a valence greater than one which will form organo-metallic compounds with the metal bonded to a carbon atom, stable toward water.

3.-The step in the method of producing a water soluble metallo-organic compound which comprises treating an organo mercuric compound having the formula R-Hg-m in whic R is'any organic radical having the Hg attached to a carbon atom in which a: is any replaceable inorganic radical or cup with a solution of an organic thio-h roxyl compound having its thio-hydroxy group directly attached to a carbon atom.

4. The method of producing a water soluble metallo-organic compound which com prises treating an organo mercuric compound having the formula. R--Hg-a: in

which R is any organic radical havin the Hg attached to a carbon atom in which :2! is any replaceable inorganic radical or group with an. alkaline solution of the thio-hydroxyl organic acid containing also a thiohydroxyl atom. 1

5. A water soluble salt of the" following acid R-H(g.-S.CH COOH in which R is an organic ra cal having the mercury directly attached to a carbon atom.

6. A water soluble salt of a compound of group directly attached to a carbon the following general formula R--M(-S'-R in which R is any organioradical group,

R is an organic radical containing an ac1d-..

oup having a replaceable hydrogen ion is a metal of a grou forming compounstable toward water with the metalbonded to a ca'rbonatom of an organic group and "Having valence ater thanl, and n is an integer greater t an 0 and at least one less than the valence ofthe metal, the metal and he 17 i e, a r n be mnded to the carbon atoms ofthe respectively.

7. A water soluble salt of a compound of mercury of the following general formula RHgSR in which R is any romatic or aliphatic group, R is an organi radical containing an acid group havin a replaceable hydrogen ion, the Hg and% atoms being bonded to carbon atoms of the R group and R group respectively. 7

S. The process of producing a water soluble mercuri-organic compound which comprises treating an organic compound of mercury of the formula R'Hg-.-w in which R is any organic radical having the mercu attached to a carbon atom and in which w is any replaceable radical or group with a water solution of an alkali metal salt of thio-glycolic acid. b

9. The process of producing a vwater soluble mercury or amc compound which comprises treating p enyl mercuric chloride with a water solution of .an alkali metal salt of thio-glycolic acid. p

10. The step in the method of producing water soluble metallo-organic com ounds, which comprises treating, in a suitab e solvent, a compound of the formula R-Ma:, in which R is any organic radical having the metal attachedvto a carbon atom, a: is any groups and R replaceable inorganic radical or grou d M is any metal which has apvalence greater than 1 and which will form organo-metallic compounds stable toward water and with the metal bonded to a carbon atom, with an organic compound containing a thiohydroxyl group and an acid-formin group and having the sulphur in the thiohydroxyl group bonded to a carbon atom. a

11. The method of producing a water soluble metallo-organic compound which comprises treating an organo mercuric compound having .the formula 3 RHg, v, in which R is any organic radical having the Hg attached to a carbon atom and in which w is any replaceable inorganic radical or group, with ail-organic com ound containing a thiohydroxyl up an anacid-forming group-and hai h g the sulphur in thethiohydroxyl group ohded to a carbon atom. t r I p 1 12. A compound containing (a)' a metal which. has a greater valence than land which will form organo-metallic comgunda nded 120 bond 13. A compound containing (a) mercurv,

an orgamc radical having a carbon atom 1omed to such mercury'by one valence bond' of the mercury, (c)' a sulphur atom joined 5 by One bond to the other valence bond of said mere and (d) an organic-acid forming/group aving a carbon atom joined to the other valence bond of the sulphur atom and when so combining wit a positive ion.

In-witness whereof I have hereunto set my hand at St. Jose h, Buchanan County, Mo.,

this 13th day of une, 1927.

MORRIS SELIG KHARASGH.

ljmoined being still capable of m 

